CN106459341A

CN106459341A - Polyester polyols from thermoplastic polyesters and dimer fatty acids

Info

Publication number: CN106459341A
Application number: CN201580023856.3A
Authority: CN
Inventors: 夏克提·L·穆科吉; 瑞克·塔博尔; 亚当·威廉·爱默生; 凯文·安东尼·罗杰斯; 埃里克·D·弗拉伯; 马修·T·布朗; 马修·J·贝蒂; 杰克·罗杰斯·科夫斯基; 迈克尔·D·凯勒曼; 迈克尔·罗伯特·克里斯蒂
Original assignee: Resinate Materials Group Inc
Current assignee: Resinate Materials Group Inc
Priority date: 2014-05-05
Filing date: 2015-04-30
Publication date: 2017-02-22
Also published as: US20150344622A1; JP6550125B2; US9840584B2; KR20170021239A; EP3140333B1; US10611879B2; US20180066106A1; BR112016025760A8; US20190241702A1; JP2017515964A; US10344121B2; EP3140333A1; WO2015171433A1

Abstract

Polyester polyols made from thermoplastic polyesters are disclosed. These polyols can be made by: a thermoplastic polyester, such as virgin PET, recycled PET, or mixtures thereof, is heated with a diol to give a digested intermediate, which is then condensed with a dimer fatty acid to give the polyol. The present invention includes a polyester polyol comprising repeating units of a glycol-digested thermoplastic polyester and a dimer fatty acid. The polyester polyol can also be produced in a single step by: reacting the thermoplastic polyester, diol, and dimer acid under conditions effective to produce the polyol. High reuse component polyols can be made that have desirable characteristics and attributes for formulating polyurethane products, including aqueous polyurethane dispersions. These polyols provide a sustainable alternative to bio-based or petrochemical-based polyols.

Description

From thermoplastic polyester and the PEPA of dimer fatty acid

Invention field

The present invention relates to the glycol composition for being produced by thermoplastic polyester, that these thermoplastic polyesters include to recycle or Without the polyethylene terephthalate for utilizing.The polyhydric alcohol knot useful for polyurethane and other condensation polymers are prepared Close dimer fatty acid.

Background of invention

Aromatic polyester polyol is these poly- amino first for manufacturing the conventional intermediate of polyurethane product Acetoacetic ester product includes soft and rigid foam, polyisocyanurate foam, coating, sealant, binding agent and elastomer. The aromatic compound composition of these polyhydric alcohol contributes to intensity, rigidity and the heat stability of the urethanes product.

Generally, the aromatic polyester polyol be by being condensed aromatic diacid, diester or anhydride (for example, terephthaldehyde Acid, dimethyl terephthalate (DMT)) manufacture with glycol (as ethylene glycol, Propylene Glycol, diethylene glycol or analog).These rise Beginning material is mostly just originated derived from petrochemistry.

With company seek more and more provide have improved sustainability product, by bio-renewable and/ Or the availability of the intermediate of the material production for recycling becomes more have leverage.However it remains for these products Needs to deliver equal or better performance compared with the petroleum base substitute which is traditional under comparable price point.

Bio-renewable composition may individually be misinterpreted as the indicant of " green " chemistry.For example, when needing food When source such as Semen Maydiss provides the bio-renewable composition, exist between charging people and their performance base chemical productss of offer clear The transaction of Chu.Additionally, in the effort of " green " state of realization compared with its petroleum base substitute, by sugar or other biological friend Good raw material is converted to useful the chemical intermediate such as chemistry of polyhydric alcohol needs or biochemical transformation and may consume more Natural resourcess and energy, and in more greenhouse gases and pollutant may being discharged to environment.

Waste thermoplastic polyester ((for example, holds from plastic beverage including waste polyethylene terephthalate (PET) stream Device)) there is provided the raw material sources for manufacturing the abundance of novel polymer.Generally, when PET is reused, it is used for manufacture New PET, PET, or it is chemically converted to produce polybutylene terephthalate (PBT).Other are again The raw material for utilizing is also obtainable.For example, the Propylene Glycol of recycling be obtainable from aircraft or RV deicing and other operations, And the ethylene glycol for recycling is obtainable from useless vehicle coolant.

Urethanes makers-up need meet for color, clarity, hydroxyl value, degree of functionality, acid number, viscosity and The polyhydric alcohol of the required specification of other characteristics.The class that these specifications will change and depending on urethanes application Type.For example, rigid foam generally requires the polyhydric alcohol for having than for manufacturing the higher hydroxyl value of the polyhydric alcohol of flexible foam.

It is suitable for the polyhydric alcohol used in manufacture high-quality polyurethane to have been proven that and be difficult to from recycling Material (including recycle polyethylene terephthalate (rPET)) manufacture.Many lists of references are described generally in catalysis RPET (being also known as " zymolysis ") is cleared up with glycol in the presence of agent such as zinc or titanium.Clear up and polymer is converted to glycol and low molecule The mixture of amount PET oligomer.Although such mixture has desirably low viscosity, they usually have high Hydroxyl value or high-caliber free diol.Frequently, target product is p-phthalic acid pair (hydroxyalkyl) ester (ginseng of purification See, for example, U.S. Patent number 6,630,601,6,642,350 and 7,192,988) or p-phthalic acid (see, e.g., the U.S. The patent No. 5,502,247).Some of zymolysis product mixtures for the effort of urethanes manufacture are described in D.Paszun and T.Spychaj survey article (Industry and engineering chemistry research(Ind.Eng.Chem.Res.)36(1997) 1373) in.

Most often, ethylene glycol is used for zymolysis as diol reactant.This is wise, because it makes possible reaction Product is minimized.Generally, zymolysis are for carrying out under the conditions of producing double (ethoxy) ester (" BHET ") of p-phthalic acid effectively, Although sometimes target is to reclaim pure terephthalic acid (PTA).When ethylene glycol is used as reactant, zymolysis product is typical at room temperature Ground is crystallization or waxy solid.Such material for as polyol intermediate be less desirable because they must rise It is processed at high temperature.It is desirably the liquid for flowing freely in room temperature or close polyhydric alcohol at room temperature.

Dimer fatty acid (being also known as " fatty acid of dimerization " or " dimeric dibasic acid ") be by catalyst (as bentonite Or montmorillonitic clay) in the presence of make unsaturated fatty acid (for example, Oleic acid, linoleic acid, castor oil acid) dimerization manufacture chemistry in Mesosome.Commercially available dimer fatty acid is typically the mixture of wherein dimeric dibasic acid product in the highest flight.Some business two Polyacids are manufactured by making ready denier oil acid dimerization.Dimer fatty acid is generally used for synthesis in ink and hotmelt Used in polyamide (see, e.g., U.S. Patent number 5,138,027).They or alkyd resin, binding agent, table Face activating agent and the component of other products.

Less typically, dimer fatty acid is used as urethanes component, especially when the urethanes During comprising the PET polylol for recycling.One exception is JP 2004-307583, which depict for producing PEPA Method with the polyurethane of solidification.It is somebody's turn to do ' 583 publications and two-step method is described, urges in ester exchange in the two-step method The PET of recycling is cleared up in the presence of agent with glycol.Then make products therefrom and there are 20 or more carbon and without polymerizable The polynary acid reaction of double bond.Dimeric dibasic acid is taught as suitable polyprotic acid for second step.Product is subsequently made with MDI Carbamate coatings of the reaction to be simple to manufacture.In working example, (every using the dimer fatty acid of relative vast scale The dimeric dibasic acid of the one or more equivalents of PET that equivalent is recycled), and whether gratifying result can be with less dimerization body fat It is unclear that fat acid is obtained.The dimer fatty acid of the vast scale also seriously limits the recycling composition in the polyhydric alcohol The amount of (recycle content) (rPET adds the glycol of any recycling).

Improved polyhydric alcohol is needs.Especially, urethanes industry is needed mostly based on recycling The continuable polyhydric alcohol of polymer (as the polyethylene terephthalate of the recycling of actual unrestricted supply).Meet poly- ammonia What color, clarity, viscosity, degree of functionality required for base Ethyl formate makers-up and hydroxy radical content were required recycles with high The polyhydric alcohol of composition will be valuable.

Summary of the invention

The present invention relates to PEPA and its manufacture method.In one aspect, the polyhydric alcohol be by including two walk Rapid method manufacture.First, by thermoplastic polyester (as PET, the PET for recycling or their mixture) together with glycol Heating is to provide the intermediate that clears up.Then the intermediate is made to be condensed with dimer fatty acid to provide the polyhydric alcohol.Another Individual aspect, the present invention relates to a kind of PEPA, thermoplastic polyester and dimer that the PEPA is cleared up comprising glycol The repetitives of fatty acid.In terms of the two, the mol ratio of dimer fatty acid and thermoplastic polyester is less than 0.8, glycol with The mol ratio of thermoplastic polyester is at least 2.0, and the polyhydric alcohol has the hydroxyl in the range of in 25 to 800mg KOH/g Number.The PEPA can also be manufactured in single step in the following manner：The thermoplastic polyester, glycol and dimeric dibasic acid is made to exist For produce the polyhydric alcohol effective under the conditions of react.Also include the aqueouss polyurethane second for being manufactured by these polyhydric alcohol Ester dispersion.

We have surprisingly found that and have for the desirable hydroxyl value for preparing polyurethane product, glue The high polyhydric alcohol for recycling composition (recycle content) of degree, outward appearance and other attributes can be manufactured in the following manner： The thermoplastic polyester (PET for preferably clearing up) for clearing up glycol is reacted with some equivalent proportions with dimer fatty acid.For Prepare various polyurethane and related product-include polyurethane dispersion, soft and rigid foam, painting Material, binding agent, sealant and elastomer-valuable polyhydric alcohol provide for bio-based or petrochemistry polylol can Lasting substitute.

Detailed description of the invention

In one aspect, the PEPA for manufacturing by two-step method is disclosed.First by thermoplastic polyester and glycol one Heating is played to provide the intermediate that clears up.The intermediate for subsequently clearing up this is polynary to provide this with dimer fatty acid condensation Alcohol.

The thermoplastic polyester for being suitable for using is well known in the art.They be by glycol and aromatic dicarboxylic acid Or the condensation polymer that the reaction of acid derivative is produced.Example includes polyethylene terephthalate (PET)；Poly terephthalic acid fourth two Ester (PBT)；Polytrimethylene terephthalate (PTT)；The polyethylene terephthalate (PETG) of glycol modification；Terephthaldehyde Acid and the copolymer (PCT) of 1,4 cyclohexane dimethanol；PCTA (PCT of isophthalate modified)；PHA, example Such as, poly butyric ester；Glycol and the copolymer of 2,5- furan dicarboxylic acid or 2,5- furan dicarboxylic acid dialkyl, for example, gather Vinyl furan acid esters；2,2,4,4- tetramethyl -1,3- cyclobutanediol is spread out with M-phthalic acid, p-phthalic acid or phthalic acid Biological copolymer；Dihydro Resina Ferulae acid polymer；And the like, and their mixture.Polyester thermoplastic's plastics another Outer example is described inModern polyester：Polyester and the chemistry and technology of copolyesters(Modern Polyesters:Chemistry and Technology of Polyesters and Copolyesters), J.Scheirs and T.Long is edited, polymer section Willie series (Wiley Series in Polymer Science) in, 2003, John Wiley father and son publishing house (John Wiley＆Sons, Ltd.), Hoboken, New Jersey (Hoboken, NJ).Other examples of thermoplastic polyester can be found inHeat Thermoplastic plastic handbook18-20 chapter (Chapters 18-20ofHandbook of Thermoplastics), O.Olabisi is edited, and 1997, Marcel moral Kerr Corp (Marcel Dekker, Inc), New York.Suitable thermoplastic poly Ester is included without the polyester for utilizing, the polyester for recycling or their mixture.Polyethylene terephthalate is particularly preferred , the polyethylene terephthalate (rPET) that especially recycles, without the PET for utilizing and their mixture.For suitable More examples of the thermoplastic polyester of conjunction, referring to U.S. Patent Application Publication No. 2009/0131625, the teachings of this application It is incorporated herein by reference.

The polyethylene terephthalate of the recycling being suitable for used in the PEPA of the manufacture present invention can be come From various sources.Modal source is the post-consumer waste stream of the PET from plastic bottle or other containers.The rPET can be Colourless or containing dyestuff (for example, green, blue or other colors) or these mixture.There may be less ratio The organic or inorganic foreign body (for example, paper, other plastics, glass, metal etc.) of example.Desirable rPET source is " thin slice " RPET, has removed a lot of usual impurities being present in waste PET bottle in advance from the rPET.Another kind of desirable RPET source is spherical rPET, and the spherical rPET is micro- to remove further by melting and extruding rPET by metal screen Grain impurity and manufacture.Because PET bottle is currently to make great efforts much bigger amount manufacture with any recycling than mating , so waste PET will continue to be obtainable in large quantities.

The glycol for being suitable for using is well-known.By " glycol ", we mean that with two or more hydroxyls Straight or branched, aliphatic or alicyclic compound or compound mixture.Other functional groups, particularly ether or ester Base is may reside in the glycol.In preferred glycol, two in hydroxyl are divided from 2 to 10 carbon, preferably 2 to 5 carbon Open.Suitable glycol includes, for example, ethylene glycol, Propylene Glycol, 1,3-PD, 1,2- butanediol, 1,3 butylene glycol, Isosorbide-5-Nitrae-fourth Glycol, 2- methyl-1,3-propanediol, tetramethylolmethane, Sorbitol, neopentyl glycol, glycerol, trimethylolpropane, 2,2,4, 4- tetramethyl -1,3- cyclobutanediol, 3- methyl isophthalic acid, 5- pentanediol, 1,4 cyclohexane dimethanol, 1,3- cyclohexanedimethanol, double Phenol A ethoxylate, diethylene glycol, dipropylene glycol, triethylene glycol, 1,6-HD, tripropylene glycol, TEG, have most Be up to about the block of Polyethylene Glycol, oxirane and the expoxy propane of the number-average molecular weight of 400g/mol or random copolymer, with And the like and their mixture.Propylene Glycol is particularly preferred.At preferred aspect, the glycol is two for recycling Alcohol, the Propylene Glycol for especially recycling.The Propylene Glycol for reclaiming from used deicing liquid is an example.

The thermoplastic polyester and glycol are optionally heated in the presence of a catalyst to provide the intermediate that clears up.This is cleared up Intermediate glycol that typically diol reactant, one or more are produced from the thermoplastic polyester, terephthalate low Polymers and the mixture of other zymolysis products.For example, when PET or rPET are the thermoplastic polyester, the intermediate that clears up Will be including diol reactant, ethylene glycol (being produced by the PET or rPET), double (2- hydroxyalkyl) esters of p-phthalic acid The mixture of (" BHAT "), higher PET oligomer and other zymolysis products.Previously manufacture and characterized in each Kind of form similar clear up mixture (see, e.g., D.Paszun et al.,Industry and engineering chemistry research (Ind.Eng.Chem.Res)36(1997) 1373 and N.Ikladious,Elastomer plastic magazine(J.Elast.Plast.)32 (2000)140).Heating is advantageously at 80 DEG C to 260 DEG C, preferably 100 DEG C to 240 DEG C, more preferably 130 DEG C to 210 DEG C and most It is preferred that carrying out at a temperature of in the range of 160 DEG C to 185 DEG C.

In one aspect, when the thermoplastic polyester is polyethylene terephthalate, the intermediate that this is cleared up includes two Alcohol and terephthalate component.The terephthalate component preferably includes by gel permeation chromatography using ultraviolet inspection Double (hydroxyalkyl) esters of the p-phthalic acid of 45 to the 70wt.% for surveying.At preferred aspect, the terephthalate component is further Terephthalate dimer comprising 20 to 40wt.%.At another preferred aspect, the intermediate that clears up to benzene two P-phthalic acid of the formic acid esters component comprising 45 to 65wt.% double (hydroxyalkyl) ester, the terephthalate two of 20 to 35wt.% The terephthalate trimer of aggressiveness and 5 to 15wt.%.In another preferred aspect, the terephthalate component P-phthalic acid comprising 50 to 60wt.% double (hydroxyalkyl) ester, the terephthalate dimers and 8 of 25 to 30wt.% Terephthalate trimer to 12wt.%.

Be applied to manufacture the intermediate that clears up catalyst be well-known (see, e.g., K.Troev et al.,Should Use polymer science magazine(J.Appl.Polym.Sci.)90(2003)1148).Especially, suitable catalyst include titanium, Zinc, antimony, germanium, zirconium, manganese or other metals.Instantiation includes Titanium alkoxides (for example, butyl titanate), titanium phosphate (IV), zirconium alcohol Salt, zinc acetate, lead acetate, cobalt acetate, manganese acetate (II), antimony trioxide, germanium oxide or analog and their mixing Thing.The catalyst for indistinctively promoting isocyanates reactive chemistry is preferred.The amount of the catalyst for being used, based on just preparing Polyhydric alcohol total amount, typically 0.005 to 5wt.%'s, preferably 0.01 to 1wt.%, more preferably 0.02 to 0.7wt.% In the range of.

Generally, it is to carry out in the following manner that this clears up reaction：Heat the thermoplastic polyester, one or more glycol, with And any catalyst liquefies at least up to the mixture and the granule of the thermoplastic polyester is no longer obvious.Reaction time range is From about 30 minutes to about 16 hours, more typically 1 to 10 hour, or even more typically 3 to 8 hours, and will be depending on reaction Temperature, the source of the thermoplastic polyester, the concrete diol reactant for being used, mixing rate, desired degree of depolymerizaton, Yi Ji Other factors in technical staff's judgement.

Glycol is at least 2.0 with the mol ratio of thermoplastic polyester, preferably 2.0 to 6.0, more preferably 2.5 to 4.5.When this two When alcohol/thermoplastic polyester mol ratio is less than 2.0, product is often solid or too viscous so that it cannot really as polyhydric alcohol Use.On the other hand, when the glycol/thermoplastic polyester mol ratio greater than about 6, hydroxyl value tends to exceed about 800mg The actual upper limit of KOH/g.

In second reaction step, the intermediate that clears up described above is made to be condensed with dimer fatty acid to provide this Bright PEPA.As it is used in the present context, " dimer fatty acid " is synonymous with " fatty acid of dimerization " or " dimeric dibasic acid ". Dimer fatty acid be by make in the presence of catalyst (as bentonite or montmorillonitic clay) unsaturated fatty acid (for example, oil Acid, linoleic acid, linolenic acid, castor oil acid) dimerization manufacture chemical intermediate.Commercially available dimer fatty acid is typically wherein The mixture of the product of dimerization product in the highest flight.Some business dimeric dibasic acids are manufactured by making ready denier oil acid dimerization 's.Dimer fatty acid frequently has 36 carbon and two hydroxy-acid groups.They can be saturated or unsaturated.They Can also be hydrogenated to remove degree of unsaturation.At preferred aspect, the dimer fatty acid includes the oil of the Oleic acid of dimerization, trimerization Acid, the linoleic acid of dimerization, the linoleic acid of trimerization, the linolenic acid of dimerization, the linolenic acid of trimerization or their mixture.Suitable Dimer fatty acid includes Pripol^TMDimer fatty acid (product of standing grain major company (Croda)), such as Pripol^TM1006、 1009th, 1010,1012,1013,1017,1022,1025,1027,1029,1036 and 1098；Unidyme^TMDimeric dibasic acid (Ya Li The product of Sang Na chemical company (Arizona Chemical)), such as Unidyme 10,14,18,22,35, M15 and M35；From meaning Mu Li oil chemistry company (Emery Oleochemicals) obtainable dimeric dibasic acid and from cottonrose hibiscus Lora chemical company The FloraDyme of (Florachem Corporation)^TMDimeric dibasic acid.

It is also known for synthesizing the method for being suitable for the dimer fatty acid for using.With at least one carbon-to-carbon double bond Fatty acid be in the presence of catalyst (as Diosmectite, Kaolin, Strese Hofmann's hectorite. or attapulgite clay) dimerization (referring to, For example, U.S. Patent number 2,793,220,4,371,469,5,138,027 and 6,281,373, the teachings of these patents are led to Cross to quote and combine here；Referring further to WO 2000/075252 and CA 104511).

Reaction between the intermediate that clears up and the dimer fatty acid be for promote in the dimer fatty Carry out under the conditions of condensation between one or more acid groups of acid and the hydroxyl that is present in the intermediate that this clears up is effective 's.The condensation preferably passes through to 230 DEG C and optimum at 80 DEG C to 260 DEG C, preferably 100 DEG C to 240 DEG C, more preferably 130 DEG C Heating at a temperature of in the range of 160 DEG C to 210 DEG C is selected to carry out.As the water for producing in this reaction is formed, advantageously will The water is removed from the reactant mixture.On a laboratory scale, it is convenient that using Dean-Stark trap (Dean- Stark trap) or similar device removing the water of reaction, but other devices will be actual on more extensive.With In water remove continuous processing, such as vacuum stripping, wiped film vaporization, and the like, it may be possible to desirable.Generally continue to this Condensation reaction, until having collected the water of scheduled volume or having reached target acid number and/or hydroxyl value for the product.

Dimer fatty acid is less than 0.8, is preferably less than 0.7, is even more preferably less than with the mol ratio of thermoplastic polyester 0.6.The mol ratio of dimer fatty acid and thermoplastic polyester is preferably in the range of 0.1 to 0.6, more preferably 0.2 to 0.5. When the mol ratio is less than 0.1, for producing useful polyhydric alcohol, (for example, hydroxyl value is useful up to or over them The upper limit) exist very little from the benefit for including the dimer fatty acid.When the mol ratio is more than 0.8, cost is prepared higher than order People is desired, recycles composition decline, and there is little or no additional performance benefit.

As long as certain dimer fatty acid is used for the polyhydric alcohol to be manufactured, one or more other dicarboxylic acids can also be included. Replace including dicarboxylic acids, it is possible to use diester or anhydride.Suitable dicarboxylic acids include, for example, 1,3-propanedicarboxylic acid, adipic acid, fourth two Acid, cyclohexane dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, 1,5- furan dicarboxylic acid, M-phthalic acid, with And its anhydride (for example, maleic anhydride, phthalic anhydride, itaconic anhydride, and the like).The mixing of dicarboxylic acids can be used Thing, including for example, being referred to as the commercially available mixture of the binary acid of " DBA ".Typical DBA compositionss can contain 51- The adipic acid of the 1,3-propanedicarboxylic acid of 61wt.%, the succinic acid of 18-28wt.% and 15-25wt.%.

Preferably, when another kind of dicarboxylic acids are included, compared with the dicarboxylic acids additional with this, the dimer fatty acid is with bigger Molar ratio exist.When the mole of dicarboxylic acids exceedes the mole of the dimer fatty acid, the polyol product has Bigger solidification is inclined to, has higher viscosity and be easy to sedimentation.

In yet another aspect, the PEPA is manufactured in single step in the following manner：Make the thermoplastic polyester, two Alcohol and dimer fatty acid for produce the polyhydric alcohol effective under the conditions of react.Many with manufactured using two-step method First alcohol is the same, and the mol ratio of dimer fatty acid and thermoplastic polyester is less than 0.8, the mol ratio of glycol and thermoplastic polyester be to Few 2.0, and the gained polyhydric alcohol has the hydroxyl value in the range of in 25 to 800mg KOH/g.When using the single -step method, Preferably with making glycol be back to reactor while allowing the condensation system of eliminating water, because remove too many glycol may result in Muddy or opaque polyhydric alcohol.Example 11 below illustrates the single -step method.

The PEPA of the present invention have 25 to 800mg KOH/g, preferably 40 to 500mg KOH/g, more preferably 200 Hydroxyl value to 400mg KOH/g.Hydroxyl value can be measured by the method for any acceptance for this kind of determination, Including, for example, ASTM E-222 (" acetylizad standard method of test (the Standard Test of use acetic anhydride for hydroxyl Methods for Hydroxyl Groups Using Acetic Anhydride Acetylation)”).

The polyhydric alcohol of the present invention preferably has 1.5 to 3.5, more preferably 1.8 to 2.5 and most preferably 2.0 to 2.4 In the range of average hydroxy functionality's (that is, average of per molecule OH group).

The polyhydric alcohol of the present invention is flowable liquid under ambient conditions.Preferably, these polyhydric alcohol have at 25 DEG C The viscosity less than 30,000cP, more preferably less than 20,000cP, more preferably less than 10,000cP of lower measurement.The polyol viscosity Preferred scope be 300 to 5,000cP, more preferably 500 to 3,900cP.The method that viscosity can be received by any industry is true Fixed.It is expedient to using the Brookfield viscometer (as the super flow graph of Brookfield DV-III) for being for example equipped with appropriate spindle and And some difference moments of torsion arrange under measuring samples with guarantee these measurement enough credibilitys.

These polyhydric alcohol preferably have low acid number.It is low that urethanes manufacturer will often require that polyhydric alcohol has Acid number in specific standard.Completed level or pass through to desired by promoting the condensation step (using dimer fatty acid) Add nertralizer (for example, sodium hydroxide) at the end of the condensation step and may insure low acid number.Preferably, these polyhydric alcohol Have less than 30mg KOH/g, more preferably less than 10mg KOH/g and the more preferably less than acid number of 5mg KOH/g.More than such as Suggestion, acceptable practice be with acid scavenger (such as epoxide derivate) adjust concrete application acid number (if ), and this process can be carried out by manufacturer, distributor or end user if necessary.

Minimizings that the advantage of these PEPAs is them on the biogenetic derivation of raw material or petrochemistry are originated according to Rely.Preferably, these polyhydric alcohol include the profit again more than 10wt.%, more preferably greater than 25wt.%, most preferably greater than 50wt.% Use composition.The preferred scope of the recycling composition is 25 to 98.5wt.%.By " recycling composition ", thermoplasticity is we mean that The amount of the combination of the glycol or dicarboxylic acids of polyester and any recycling.Some glycol (as Propylene Glycol or ethylene glycol) are used as recovery Or the material for recycling is obtainable.For example, Propylene Glycol is used in deicing liquid, and after use, and it can be recovered, pure Change and reuse.Generally, the dimer fatty acid is prepared from Renewable resource.Recycle composition can for example pass through with Under type is calculated：The quality of the dicarboxylic acids of the PG or recycling of thermoplastic polyester and any recycling is merged, by this summation Divided by the gross mass of reactant (glycol, thermoplastic polyester, dimeric dibasic acid and any dicarboxylic acids), and and then result is multiplied by 100.

Although the performance in terms of last final use is most important, urethanes manufacturer likes buying Seem good polyhydric alcohol.When other considerations are equal, transparent (or nearly transparent) polyhydric alcohol may be than impermeable Bright polyhydric alcohol more attractive.(carrying used in automotive seat or furniture applications, high resilience urethanes bubble " the dispersion polyhydric alcohol " of the usual ingredients of foam or " polymer polyatomic alcohol " are noticeable exceptions；They are assumed to be and seem not Transparent.) product is cleared up with dicarboxylic acids such as succinic acid or phthalic anhydride system unlike known by making thermoplastic polyester Opaque polyhydric alcohol making, often, the polyhydric alcohol of the present invention is often transparent or nearly transparent.When glycol and heat When the mol ratio of plasticity polyester is maintained in the range of 2.5 to 4, especially so.

Another kind of desirable polyhydric alcohol attribute is not the presence of sedimentation again, particularly in the storage for extending.Work as sedimentation When being substantial amounts of, the polyhydric alcohol may must be filtered out or be treated to remove solid constituent otherwise；This is preferred Be avoided by.The polyhydric alcohol of the preferred present invention does not show sedimentation or shows the sedimentation of only slight extent, and more excellent The polyhydric alcohol of choosing does not show the evidence of sedimentation.

In yet another aspect, the present invention includes a kind of PEPA, the thermoplastic that the PEPA is cleared up comprising glycol Property polyester and dimer fatty acid repetitives, the wherein mol ratio of dimer fatty acid and thermoplastic polyester is less than 0.8, two Alcohol is at least 2.0 with the mol ratio of thermoplastic polyester, and the polyhydric alcohol has the hydroxyl in the range of in 25 to 800mg KOH/g Radix.It is described above thermoplastic polyester and dimer fatty acid that the glycol is cleared up." repetitives " refer to the polyester Polyhydric alcohol is one or more comprising each of the thermoplastic polyester that clears up derived from the dimer fatty acid and the glycol Unit.

In particular aspects, the present invention relates to a kind of method, the method includes：A () will not in the presence of zinc or titanium catalyst PET, the PET for recycling or their mixture through utilizing is heated to provide the intermediate that clears up together with Propylene Glycol；And B () makes the intermediate be condensed with dimer fatty acid to provide the polyhydric alcohol；Wherein dimer fatty acid is little with the mol ratio of PET In 0.6, the mol ratio of glycol and PET is that and the polyhydric alcohol has in 40 to 500mg KOH/g in the range of 2.5 to 4.5 In the range of hydroxyl value, less than 25 DEG C of 5,000cP at viscosity and if definition herein is more than 25wt.%'s Recycle composition.

The PEPA of the present invention can be used for preparing diversified polyurethane product.By adjusting institute The ratio of the dimer fatty acid for using, the polyhydric alcohol hydrophobicity of desired degree is possible " being dialled in (dialed in) ".Control Hydrophobic ability is especially valuable in coatings industry.These polyhydric alcohol can be used for porous, micropore and non-porous Application, these application include flexible foam, rigid foam (including polyisocyanurate foam), urethane dispersion, Coating, binding agent, sealant and elastomer.Gained polyurethane for automobile and transport applications, building products, Marine product, packaging foam, flexible slabstock foam, carpet backing, utensil insulation, cast elastomer and mechanograph, footwear, biology Medical Equipment and other application are potentially usefuls.

Further, by with the derivative raw material esterification of acrylic or methacrylic acid or ester exchange can with derivatization this Bright PEPA is to form single-, two- and polyacrylate.It is applied to (methyl) of the PEPA for forming the present invention The example of (methyl) of acrylate derivative acrylated raw material include acryloyl chloride, methacrylic chloride, methacrylic acid, Acrylic acid, acrylic acid methyl ester., methyl methacrylate, and the like or their mixture.Such (methyl) acrylic acid The PEPA of the present invention derived from ester is useful for radiation or the coating material solidified preparation of UV or application.By with (first Base) 2-(Acryloyloxy)ethanol reaction can be with the prepolymer of the PEPA of the derivatization present invention to form urethanes (first Base) acrylate.Gained urethaneacrylates are can be used in radiation or the coating material solidified preparation of UV or application.

At specific aspect, the present invention relates to the aqueouss polyurethane for being manufactured by the PEPA of the present invention divides A prose style free from parallelism.We have found that the modified polyhydric alcohol of dimer fatty acid is easily formulated into the aqueouss with desirable balance of properties Polyurethane dispersion, these characteristics include high solid, low viscosity and low sedimentation tendency.The poly- ammonia of configuration aqueouss Many modes of base Ethyl formate dispersion are known and are adapted for use with.Preferably, the polyurethane dispersion Be by helping in emulsifying agent under in water isocyanate emulsion end-blocking prepolymer manufacture.Water, water-soluble polyamine expand Chain agent or combinations thereof can be used for reacting with the prepolymer of the emulsifying.The prepolymer is preferably made in the following manner Make：Make the PEPA of the present invention, the emulsifying agent of hydroxyl-functional, one or more auxiliary polyhydric alcohol and one or more Polyisocyanate is reacted.These aqueouss polyurethane dispersions be preferably used for prepare water based paint, binding agent, Sealant, elastomer and similar urethanes product, and they are especially have for the dependence to solvent is reduced It is worth.For example, these dispersions can be used for preparing the compositionss of low VOC or Diamond Search.

The polyisocyanate being suitable for used in these prepolymers are manufactured is well-known；They include aromatic series , aliphatic and alicyclic polyisocyanate.Example includes toluene di-isocyanate(TDI) (TDI), MDI, the MDI of polymerization, naphthalene Diisocyanate (NDI), the MDI of hydrogenation, trimethyl-or tetramethyl hexamethylene diisocyanate (TMDI), hexa-methylene two Isocyanates (HDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (CHDI), two isocyanide of xyxylene Acid esters (XDI), hydrogenation XDI, and the like.Aliphatic diisocyanate such as hexamethylene diisocyanate and isophorone Diisocyanate is particularly preferred.

The auxiliary polyhydric alcohol for being suitable for using is also well-known.They include that polyether polyol, aliphatic polyester are many First alcohol, aromatic polyester polyol, polycarbonate polyol, glycol, and the like.Preferred auxiliary polyhydric alcohol has 2 Average hydroxy functionality in the range of 6, preferably 2 to 3, and 500 to 10,000, preferably 1,000 to 8,000 scope Interior number-average molecular weight.Preferred PEPA is dicarboxylic acids and glycol or triol (for example, ethylene glycol, Propylene Glycol, 2- first Base -1,3- Propylene Glycol, 3- methyl isophthalic acid, 5- pentanediol, 1,4- butanediol, neopentyl glycol, glycerol, trimethylolpropane, 1,4- Cyclohexanedimethanol, bisphenol A ethoxy thing), the condensation product of especially glycol.These dicarboxylic acids can be aliphatic (example Such as, 1,3-propanedicarboxylic acid, adipic acid, succinic acid) or aromatic (for example, phthalic acid), preferred aliphat.

The emulsifying agent of hydroxyl-functional is also used for manufacturing these polyurethane dispersions.The effect of this component is logical Often based on its combination with water and nertralizer (as acid or base reactants), water-dispersible is given the prepolymer.Therefore, exist On one side, the emulsifying agent of the hydroxyl-functional is the glycol of sour sense, such as dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA).The acid functionality of gained prepolymer allows to be neutralized with amine or other alkaline reactants to produce the dispersible amino first of water Acetoacetic ester.The emulsifying agent of the hydroxyl-functional can also be amine, such as N methyldiethanol amine.With in acid reagent and gained prepolymer It is that water is dispersible to cause which.In other respects, the emulsifying agent of the hydroxyl-functional be non-ionic, for example, polyethyleneglycol first Ether.In yet another aspect, the emulsifying agent of the hydroxyl-functional can be poly- (oxirane) of single methanol-or glycol-functionalization, for example As Ymer^TMN120 dispersed monomer (product of Paasche support company (Perstorp)) or the methyl ether of Polyethylene Glycol.Additionally, non-anti- Answering property, so-called " external emulsification agent ", the such as triethanolamine salt of DBSA, can be contained in side in water phase Help emulsifying and stablize the prepolymer and gained polyurethane dispersion.

In some aspects, chain terminating agent can be used for controlling and be included in internal poly- of aqueouss polyurethane dispersion The molecular weight of urethane polymers.There is the compound of the simple function containing single-activity hydrogen group, such as containing hydroxyl, Those of amino and mercapto groups, are suitable chain terminating agents.Example include alcohol, amine, mercaptan, and the like, especially uncle and Secondary fatty amine.

In the polyurethane dispersion is manufactured, chain extender can also be included.In some respects, be enough to make The amount of the dissociateive NCO group reaction of the presence of 5 to 105 moles of % adds the chain extender.Suitable chain extender contains at least two Can be with functional group's (for example, in any combination of hydroxyl, sulfydryl or amino group) of isocyanates reaction.Suitable chain extender Including, for example, glycol (ethylene glycol, Propylene Glycol, diethylene glycol, neopentyl glycol, BDO, 2- methyl isophthalic acid, ammediol, 3- methyl isophthalic acid, 5- pentanediol, 1,4 cyclohexane dimethanol, and the like), diamidogen and polyamine (ethylenediamine, diethylidene three Amine,T-403、D-230、ED-2001、ED-600、ED-900,1,6- hexamethylene diamine, butanediamine, hydrazine, piperazine, N-hydroxyethyl-ethylenediamine), alkanolamine (ethanol Amine, diethanolamine, N methyldiethanol amine, and the like), two mercaptan, and the like.Preparation process in the prepolymer In and in water before emulsifying, preferably add diol chain-extension agent.

In instantiation described below, by modified for dimer fatty acid PEPA, the glycol of sour sense (DMPA) and auxiliary polyhydric alcohol (polyethylene glycol 200 and by 3- methyl isophthalic acid, the polyester of 5- pentanediol and adipic acid manufacture Polyhydric alcohol) combine and mixed with aliphatic diisocyanate (hexamethylene diisocyanate and isophorone diisocyanate) Compound is carried out in the presence of tin catalyst (dibutyl tin laurate) or bismuth catalyst (as two Bismuth Octoates) and solvent (acetone) Reaction.Then gained prepolymer is scattered in the mixture of water, triethanolamine (nertralizer) and silicone antifoams agent.Products therefrom It is the aqueouss polyurethane dispersion with highly filled (30%), low viscosity and desirable settling character Body.

For the more examples for preparing the suitable approach of aqueouss polyurethane dispersion, referring to United States Patent (USP) Numbers 5,155,163；5,608,000；5,763,526；6,339,125；6,635,723、7,045,573；With 7,342,068, this The teachings of a little patents are incorporated herein by reference.

In yet another aspect, the present invention relates to the associativity stream for being manufactured by the modified PEPA of the dimer fatty acid Become modifying agent.By " associativity rheology modifier ", the additive for thickening or the viscosity for changing product is we mean that.Associate Property thickening can relate to thickener molecule with itself and non-specific with the dynamic of the hydrophobic ending group of the other components of preparation Interact.Associativity thickening is particularly applicable to water base japanning and coating, wherein the rheology modifier by intermolecular and Intramolecular network is formed and can change gloss, flowing, shearing, levelling, resistance to splashing property or other characteristics.Except japanning or coating it Outward, suitable preparation may include to have benefited from rheology modified sealant, medicine, cosmetics or other products.Some classes Other associativity rheology modifier be it is well known that and can use the present invention PEPA (individually or more often Often combine with other polyol components) prepared.Such rheology modifier includes, for example, the ethoxylation of hydrophobically modified Urethanes (" HEUR "), the alkali swellable emulsion (" HASE ") of hydrophobically modified and the polyethers of hydrophobically modified (“HMPE”).Suitable HASE modifying agent includes, for example, the polyacrylate of hydrophobically modified.Typical HEUR can be from hydrophilic Property glycol (Polyethylene Glycol of for example, 6,000-8,000g/mol), polyisocyanate and hydrophobicity single methanol or glycol assembling.This The PEPA of invention can be used for augmenting or replacing the hydrophobicity single methanol or glycol.HEUR, HASE and HMPE are associated Property rheology modifier and the example of their preparation method, referring to U.S. Patent number 8,871,817；8,673,275；8,697, 797；8,524,649；8,461,213；8,334,357；6,337,366；5,574,127；5,281,654；4,155,892；With 4,079,028, the teachings of these patents are incorporated herein by reference.

Following instance only illustrates the present invention；Technical staff will be recognized that the scope in spirit and claims of the present invention book Interior many changes.

The preparation of the modified polyhydric alcohol of dimer fatty acid：General program

Load acetic acid in the reactor equipped with top-type blender, condenser, heating mantle, thermocouple and nitrogen entrance Zinc dihydrate (0.55wt.%), butanol titanium (IV) (500-1000ppm) or without catalyst (example 32)；Recycled is poly- PETP pellet；And glycol (ratio to illustrate in table 1).Under no stirring, by the mixture heating To about 130 DEG C.Then stirring is started with 60rpm, and heats and be continued until that reactor content reaches 180 DEG C.Heat this to mix Compound leaves (about 4h) until not having the PET granule for recycling.When it is considered as to complete that this clears up reaction, will be cold for the mixture But to about 100 DEG C.Add dimer fatty acid (and/or dicarboxylic acids) (for mol ratio referring to table 1), and improve mixing rate (200rpm).The product Pripol of the dimer fatty acid Shi He major company for being used^TM1017.When the interpolation is completed, at this Dean-Stark trap is introduced between reactor and condenser, and restarts to be heated to 200 DEG C.Remove in the condensation The water for producing in reaction is until substantially eliminating theoretical amount.When the reaction is completed, the polyol product is allowed to cool to 100 DEG C and and then be decanted from the reactor and filtered by coarse sheeting.

The glycol for being used is Propylene Glycol, 2- methyl-1,3-propanediol, 3- methyl isophthalic acid, 5- pentanediol, diethylene glycol, with And 1,4 cyclohexane dimethanol.In most of example, as described above, cleared up with the glycol recycling PET it Afterwards, add the dimer fatty acid (and/or dicarboxylic acids).In several instances, however, start when (that is, before clearing up) add Plus the dimer fatty acid (and/or dicarboxylic acids).Also include controlled trial, without using dimer fatty acid or dicarboxyl Acid.In some instances, the dicarboxylic acids are " DBA ", mainly contain 1,3-propanedicarboxylic acid, succinic acid and adipic acid from English Radar Audio Company And the obtainable well-known diacid blend of other suppliers (INVISTA).Typical DBA compositionss can contain 51- The adipic acid of the 1,3-propanedicarboxylic acid of 61wt.%, the succinic acid of 18-28wt.% and 15-25wt.%.Used dicarboxylic acids (or acid Acid anhydride) it is succinic acid, phthalic anhydride, adipic acid and DBA.These are catalyzed by zinc acetate to clear up, unless in addition referred in table Bright.

" recycling composition " (wt.%) determines in the following manner as used in this article：By recycle glycol and The quality of the thermoplastic polyester of recycling merges, and this summation (for example, glycol, rPET, dimeric dibasic acid and is appointed divided by reactant What dicarboxylic acids) gross mass, and and then result is multiplied by 100.

Hydroxyl value and acid number are determined by standard method (accordingly ASTM E-222 and ASTM D3339).

Viscosity be at 25 DEG C using the super flow graph of Brookfield DV-III with spindle #31 25%, 50%, With measurement under 75% moment of torsion.

Visual assessment color, clarity and sedimentation degree.

As a result：

As shown in table 1 and 2, with the hydroxyl value less than 800mg KOH/g (particularly less than 600mg KOH/g), have The viscosity (especially 1000 to 4000cP) of profit and the polyhydric alcohol of the recycling composition more than 10wt.% (especially greater than 25%) Can be by making PET and the manufacture of dimer fatty acid reaction of recycling that glycol clears up, the mol ratio of wherein glycol and rPET It is at least 2.0 and the mol ratio of dimer fatty acid and rPET is less than 0.8.The rPET for clearing up the glycol and dimer fatty Acid condensation also allows to produce polyhydric alcohol, and these polyhydric alcohol are transparent in many cases, especially as the glycol and rPET When mol ratio is in the range of 2.5 to 4.5.If desired, some dicarboxylic acids (for example, succinic acid) can in company with this two Dimer fatty acids are included together, but such product is typically opaque.Generally by using preferred 2.5 to 4.5 glycol avoids sedimentation with rPET molar ratio range.

Comparison example is provided in table 3 and 4.In some comparison example, the glycol/rPET ratio is less than 2.0, this typical case Ground causes the product of the viscous or solid of opaque and height.In other comparison example, the glycol/rPET ratio be 2.0 or Bigger, but eliminate the dimer fatty acid replace with dicarboxylic acids or anhydride (for example, succinic acid, phthalic anhydride or DBA).Product is opaque and is intended to viscous.When the glycol/rPET ratio is high (6.0 or 9.0), product Hydroxyl value be more than 800mg KOH/g.Other comparison example show individually to clear up the rPET and give to have makes us wishing The product of the low viscosity in ground, but hydroxyl value is too high and to not be useful.

Aqueouss polyurethane dispersion

The modified polyhydric alcohol of DFA as prepared in example 30 is used for following preparation polyurethane dispersion：

By by modified for the DFA polyhydric alcohol (53.4g), P2010 polyhydric alcohol (3- methyl isophthalic acid, 5- glycol adipate, 2000mol.Wt., 17.1g, the product of Kuraray company (Kuraray)), neopentanoic acid (9.5g), Polyethylene Glycol (PEG 200,1.33g), acetone (140g) and dibutyl tin laurate (0.24g) and hexamethylene diisocyanate (8.8g) and different Isophorone diisocyanate (64.8g) combines to produce prepolymer.The mixture is sufficiently mixed and is allowed at 60 DEG C anti- 7.5h should be continued to form pre-polymer mixture.

By the pre-polymer mixture (261g) and water (456g), triethanolamine (14.4g) and028 silicone antifoams Agent (10% solution in water of 6.21g) is combined and is promptly mixed to produce aqueouss polyurethane dispersion. Gained pale green dispersion has 29.7% solid, the viscosity=809cP at pH=8.05 and 21.5 DEG C.

The modified polyols preparation of 1. dimer fatty acid of table：The example of the present invention

Sedimentation experiment

Polyurethane dispersion made above is filtered by 190- μm of japanning filter and is filtered to heavy In drop circular cone body.The cone is used" M " lab membrane is sealed and storage continues 19 days in camera bellows.In knot After restrainting the sedimentation period, the dispersion is shown without significantly settling (about 0.0mL).

Prepared by the polyethylene terephthalate (0.9 Propylene Glycol and 1rPET) of the recycling that is cleared up by glycol and not There is after 19 days the material of 0.4mL sedimentation with the modified similar polyurethane dispersion of dimer fatty acid.

Acrylate from the modified polyhydric alcohol of DFA-

Load dimerization body fat in equipped with charging hopper, condenser, heating mantle, thermocouple and churned mechanically flask The fat modified polyhydric alcohol of acid (75.0g, as described above from the polyethylene terephthalate (28.3wt.%) for recycling, third Glycol (31.4wt.%), butanol titanium (IV) (0.5wt.%) and Pripol^TM1017 dimer fatty acid (39.8wt.%) Produce), tetrahydrofuran (300mL), triethylamine (50.8g) and phenothiazine (0.19g).The mixture of the stirring is heated to 50℃.Resulting solution is cooled to 10 DEG C, and adds acryloyl chloride (44.8g) in 2h.Stirring continues for other 1h.Will Products therefrom passes through545 filter aids are filtered to remove the triethylamine salt acidulants of precipitation.Filtrate is stripped under vacuo And it is re-dissolved in dichloromethane (350mL).Will be water-soluble to NaOH aqueous solution of the organic faciess with 10% and then the NaCl with 10% Liquid is washed, and then dries (MgSO₄) and concentrate (40 DEG C -60 DEG C, 70mm Hg).Yield：84.6g.¹The analysis of H NMR spectra is shown Gone out to the conversion of acrylate ester be completely.

Acrylate paint

Coating is produced using the modified polyalcohol acrylate of DFA described above and control preparation.The control is prepared Product (50wt.% solid in methyl ethyl ketone (MEK)) be from bisphenol A ethoxy thing diacrylate (66.5wt.%), second Glycol phenyl ether acrylate (26.5wt.%), Addox^TMA40 adhesion promotor (5.0wt.%, when degree chemical company (Doxa Chemical product)) andPrepared by 1173 light triggers (2.0wt.%, product of BASF AG (BASF)) 's.The modified polyalcohol acrylate preparation of DFA (50wt.% solid in MEK) be from bisphenol A ethoxy thing dipropyl Olefin(e) acid ester (37.1wt.%), ethylene glycol phenyl ether acrylate (15.9wt.%), the modified polyalcohol acrylate of DFA (40wt.% is prepared as previously discussed), Addox^TMA40 adhesion promotor (5.0wt.%) and1173 light Prepared by initiator (2.0wt.%).Calendered film is to provide the coating of the solidification of the average film thickness with 1.6-1.8 mil.This A little coating are solidified in the following manner：Four times by the hand-held UV cure lamp of Jelight then in the UV for being operated with 5ft./min Bench-top conveyer unit (congratulating Li Shi special source company limited (Heraeus the Noblelight)) last time passes through.Knot Fruit is come across in table 5.

Method of testing for acrylate paint：

Determined using PosiTector 6000 (Di Fusigao company (Defelsko Corporation)) elcometer Build.Konig hardness (Konig is measured using ISO 1522 using TQC pendulum hardness tester (model SPO500) hardness).Using following ASTM Test Method：Pencil hardness：ASTM D3363；Flexible：ASTM D522；Adhesiveness：ASTM D3359；Coloring test：ASTM D1308.

Rigid foam from the modified PEPA of dimer fatty acid

By make dimer fatty acid polylol (mol.wt.500, hydroxyl value=224mg KOH/g, 70.4wt.%, As previously described from the PET (28.7wt.%) for recycling, Propylene Glycol (31.9wt.%), dimer fatty acid (39.3wt.%) prepare with butanol titanium (IV) (0.10wt.%)) and Fyrol^TMPCF fire retardant (8.0wt.%, Israel Learn the product of company limited (Israel Chemical Ltd.)),K-15 catalyst (1.60wt.%, air products Company (Air Products)),5 catalyst (0.13wt.%, Air Products Company),B8465 silicon Ketone surfactant (2.6wt.%, Ying Chuan company (Evonik)), water (0.32wt.%) and pentane (18.3wt.%) mixing Until uniform big plastic beaker (6 " diameter, 5 " high) in combination " part B " component.These percentage ratios be based on part B component Amount.

Then rapidly add by PAPI^TM27 isocyanates (MDI of polymerization, the combined amount based on part A and B 53.3wt.%, 260NCO/OH index, the product of Dow Chemical (Dow Chemical)) " the part A " that constitute.By portion After in dividing A to add to part B, immediately the container is placed on the VOS equipped with 3- inch diameter Cowles blade Power Control blender (VWR international corporation (VWR International)) is upper and mixes under up to 2000RPM lasting Ten seconds.The incorporation time is controlled by the electronic timer (GraLab model 451) with pedal adnexa.Stop in mixing Afterwards, 12 are poured into immediately the well-mixed foam " x12 " x12 " and carton in and allow rise.Under ambient conditions After being fully cured, compressive strength (ASTM D1621) and the thermal conductivity (ASTM C177) of these foams are tested.

Previous examples are provided merely as explanation；Following claims limits subject of the present invention.

Claims

1. a kind of PEPA, is manufactured by the following method, and the method includes：

A () heats thermoplastic polyester to provide the intermediate that clears up together with glycol；And

B () makes the intermediate be condensed with dimer fatty acid to provide the polyhydric alcohol；

The mol ratio of wherein dimer fatty acid and thermoplastic polyester is less than 0.8, the mol ratio of glycol and thermoplastic polyester be to Few 2.0, and the polyhydric alcohol has the hydroxyl value in the range of in 25 to 800mg KOH/g.

2. polyhydric alcohol as claimed in claim 1, the wherein thermoplastic polyester is selected from the group, and the group is made up of the following：Poly- PETP；Polybutylene terephthalate；Polytrimethylene terephthalate；The poly- terephthaldehyde of glycol modification Sour second diester；P-phthalic acid and the copolymer of 1,4 cyclohexane dimethanol；The p-phthalic acid of isophthalate modified and 1, The copolymer of 4- cyclohexanedimethanol；PHA；Glycol and 2,5- furan dicarboxylic acid or 2,5- furan dicarboxylic acid dioxane The copolymer of base ester；2,2,4,4- tetramethyl -1,3- cyclobutanediol is spread out with M-phthalic acid, p-phthalic acid or phthalic acid Biological copolymer；Dihydro Resina Ferulae acid polymer；And their mixture.

3. the polyhydric alcohol as described in claim 1 or claim 2, the wherein thermoplastic polyester is selected from the group, and the group is by following Every composition：Without the PET for utilizing, the PET for recycling and their mixture.

4. polyhydric alcohol as claimed any one in claims 1 to 3, the wherein glycol is selected from the group, and the group is by the following group Become：Ethylene glycol, Propylene Glycol, 1,3- Propylene Glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2- methyl isophthalic acid, 3- the third two Alcohol, tetramethylolmethane, Sorbitol, neopentyl glycol, glycerol, trimethylolpropane, 2,2,4,4- tetramethyl -1,3- ring fourth two Alcohol, 3- methyl isophthalic acid, 5- pentanediol, 1,4 cyclohexane dimethanol, 1,3- cyclohexanedimethanol, bisphenol A ethoxy thing, diethyl two Alcohol, dipropylene glycol, triethylene glycol, 1,6-HD, tripropylene glycol, TEG, have the up to about number of 400g/mol equal The Polyethylene Glycol of molecular weight, the block of oxirane and expoxy propane or random copolymer and their mixture.

5. the polyhydric alcohol as any one of Claims 1-4, the wherein glycol include the glycol for recycling.

6. the polyhydric alcohol as any one of claim 1 to 5, with the hydroxyl in the range of 40 to 500mg KOH/g Number.

7. the polyhydric alcohol as any one of claim 1 to 6, the wherein dimer fatty acid and thermoplastic polyester mole Than being less than 0.6.

8. the mol ratio of the polyhydric alcohol as any one of claim 1 to 7, the wherein glycol and thermoplastic polyester be In the range of 2.5 to 4.5.

9. the polyhydric alcohol as any one of claim 1 to 8, with the viscosity at 25 DEG C less than 10,000cP.

10. a kind of transparent as claimed in any one of claims 1-9 wherein polyhydric alcohol.

11. polyhydric alcohol as any one of claim 1 to 10, with definition such as herein more than 50wt.%'s Recycle composition.

12. polyhydric alcohol as any one of claim 1 to 11, wherein make the intermediate and the dimer fatty acid and Binary acid or anhydride condensation.

13. polyhydric alcohol as claimed in claim 12, the wherein binary acid or anhydride are selected from the group, and the group is by the following group Become：1,3-propanedicarboxylic acid, adipic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, M-phthalic acid, 1,5- furan two Carboxylic acid, maleic anhydride, phthalic anhydride, itaconic anhydride and their mixture.

14. polyhydric alcohol as any one of claim 1 to 13, wherein heat the thermoplastic polyester in the presence of a catalyst And glycol.

15. polyhydric alcohol as claimed in claim 14, the wherein catalyst are zinc acetate or butyl titanate.

16. polyhydric alcohol as any one of claim 1 to 15, wherein in the range of 80 DEG C to 260 DEG C at a temperature of Heat the thermoplastic polyester and glycol.

17. polyhydric alcohol as any one of claim 1 to 16, the wherein dimer fatty acid include dimerization Oleic acid, The linoleic acid of the Oleic acid, dimerization of trimerization, the linoleic acid of trimerization, the linolenic acid of dimerization, the linolenic acid of trimerization or their mixing Thing.

18. polyhydric alcohol as any one of claim 1 to 17, with the acid number less than 10mg KOH/g.

A kind of 19. PEPAs, are manufactured by following method, and the method includes：Make thermoplastic polyester, glycol and dimerization Body fat acid reaction is to produce the polyhydric alcohol, and the mol ratio of wherein dimer fatty acid and thermoplastic polyester is less than 0.8, glycol with The mol ratio of thermoplastic polyester is at least 2.0, and the polyhydric alcohol has the hydroxyl in the range of in 25 to 800mg KOH/g Number.

A kind of 20. PEPAs, the thermoplastic polyester that clears up comprising glycol and the repetitives of dimer fatty acid, wherein two Dimer fatty acids are less than 0.8 with the mol ratio of thermoplastic polyester, and glycol is at least 2.0 with the mol ratio of thermoplastic polyester, and The polyhydric alcohol has the hydroxyl value in the range of in 25 to 800mg KOH/g.

A kind of 21. polyurethane, by the polyhydric alcohol manufacture as any one of claim 1 to 20.

A kind of 22. two components polyurethane coating, by the polyhydric alcohol system as any one of claim 1 to 20 Make.

A kind of 23. aqueouss polyurethane dispersions, by the polyhydric alcohol system as any one of claim 1 to 20 Make.

A kind of 24. coating, are manufactured by aqueouss polyurethane dispersion as claimed in claim 23.

A kind of 25. curable resins, arbitrary with such as claim 1 to 20 comprising acrylate or methacrylate source The product of the polyhydric alcohol described in.

A kind of 26. coating of UV solidification, by resin manufacture as claimed in claim 25.

A kind of 27. rigid polyurethane foams, by the polyhydric alcohol manufacture as any one of claim 1 to 20.

A kind of 28. methods, the method includes：

B () makes the intermediate be condensed with dimer fatty acid to provide PEPA；

A kind of 29. methods, the method includes：Make thermoplastic polyester, glycol and dimer fatty acid reaction polynary to produce this The mol ratio of alcohol, wherein dimer fatty acid and thermoplastic polyester is less than 0.8, the mol ratio of glycol and thermoplastic polyester be at least 2.0, and the polyhydric alcohol has the hydroxyl value in the range of in 25 to 800mg KOH/g.

A kind of 30. methods, the method includes：

A () is by without the PET for utilizing, the PET for recycling or their mixture together with Propylene Glycol in the presence of titanium catalyst Heating is to provide the intermediate that clears up；And

The mol ratio of wherein dimer fatty acid and PET is less than 0.6, and the mol ratio of glycol and PET is the scope 2.5 to 4.5 Interior, and the polyhydric alcohol has gluing at the hydroxyl value in the range of 40 to 500mg KOH/g, 25 DEG C less than 10,000cP Degree and the recycling composition more than 25wt.% as herein definition.

A kind of 31. PEPAs, by the method manufacture as any one of claim 28 to 30.

A kind of 32. associativity rheology modifiers, by the polyhydric alcohol as any one of claim 1 to 20 or claim 31 Manufacture.

33. rheology modifiers as claimed in claim 32, the rheology modifier is selected from the group, and the group is made up of the following： The urethanes of the ethoxylation of hydrophobically modified, the alkali swellable emulsion of hydrophobically modified and the polyethers of hydrophobically modified.